Manufacture of sized, filled paper



MANUFACTURE, onsl'zltn rjn gnnp David 'e, Freeport, N. Y., or .=to:tA nierican' -CfyM d Company NewzYork, NiY ncorporation me p a a The present inventiongirelates to-theimanufacture of the beater addition process; The-ginvention; includes a such as rosin size, alone or in'conjunction with (waxs ze," S v are best precipitated from-water containing a minimum amount of f dissolved sulfate ionsand are not precipitated well .from water gcontaining mQr'e thamabQiItqSOOV-WO parts per million of dissolved sulfategions it evident ieithertheitgthe; manufactureot: sizedpaper-generally i's' not nowperformedundersoptimumconditions; or that ment, particularly. thegwirq becomessubjected nto coi rosionand the-rv' v'ater 'resistance of ;the=papenobtainedi de'- creases. Moreovergwhere a wet strengthiiresin is'added, the; gsultate ions -;inhibit -.adsorption of the" resin iby the sized, filled paper and sized, ;filled;wet-strength papenby method for utilizing the dissolved sulfate ion content of I paper mill whitewater systemswhile producing, rosin sized papers including rosin-sized wet strength ipapers containing barium sulfate, aluminumhydrate and, if-desired, aluminum phosphate as fillers. Theginventio'nifurther includes a method-for'maintaining thegdissolved sulfate ion content substantially constantin' closed or substantially closed paper mill water systems; that is, systems in which more than about60 %580% ,o the white water is recycled-.3 I ,1 o Ordinary sized -1paperis generally manufactured by forming a dilute aqueous suspension of paper-making cellulosic fibers atabetween about .'/2% to 1% consistency,

adding liquid rosin or other soapfsize vthereto, precipitating .the sizing material ongthe fibers by; thegaddition of alum-,and sheetingithe fibersonga; wire screen Fhe water employed to suspend the, fibers drains throughgthe screen, and the cellulosicweb'onathe'screen is heated and dried to formpaper paperboard;etci g; 3 So far as is practieal, the W3 t f df ail 'lin8 th screen is recycled: to form n freslrsuspensionof cellulose fibers. It is found, however,-that as the watemisrecycled it contains increasing. amounts of aluminum and sulfate ions for the following -reasons.5 vThe theoretical equation; for-the rougih the f undersize cellulose ti bariumsulfate (is; formed. as crystal large amounts ,"ofgwater-containing substantial aluminum and sulfatevalues are; allowed to :go-to.waste.f;;-,-

Asthe water; is reu'sed,.-ultimately thei-concentratio of 1 gsulfatetionsbecomesso high thatthe paper-maki r ij.

ceillulosefibers resulting information of; paper-oi deficient wet "strength (cf. Maxwell et aL. U S: Patent-No12,5199,-

221 y. alt -is 'generaL-practice; "therefore, to continuously the aluminum and sulfate ions dis'solvedtherein.

F t m r tthe hi sfl watsriw a n ha he re n t; s fibrous suspensionis -s t.d-j- V fibers, lost whenthe' white waterissentto-waste;.

g( cf.- Lu-Sc Patent No not proved practical barium;chloride'is-eostly; r

sgi oi small, as to :be;

substantially: untilterable. As-a resultyqsubstantially Tail 7 the barium chloride added flows; outwith the -whitevwate;

principally as barium sulfate and'does'not increase' -the t 5pm i y (as sodium rosinate) ;wi th-aluminum sulia fiyindicates that the aluminumisulfatei is split, the alumirium ions being in lu z qebvl-s sam inati n.zwith' t e. 5 9 m a s s nt wh e-;th. su iateaiq Em solution as sodium sulfate. Moreover, paper isfprac ally always sizedt with at least y; %r and usually .1 3% of rosin size based on the lweight of the--fib ers,-. an

jahim to a new principally on the type the stock; the dissofied iodidm ionebneemrationiucrew ing atthe much slowei rate'ofs'about 7,25 parts per mih lion. The dissoivettiutfa't'eion content-of theiwater-thus continuously rises as tiie water; Er'eused, an'dmince fresh river and well-waters firequently contain";slti stantia;l x concenttations of; sulfatet ion values of -450 p r s per on-be n nadibs lv desfl nzvw s mrah weight of alum added is customarily 150%,912 m 're..of.

na et hi evide fthat c'qnstitucame-mean a suspension of e he d a lh sa s at {s s nb m m tm nns Wi s; e d-dr e m ut th on the-fibers,

tions .as high as loih parts per million have Beenobserved in actual mill -capefatiohs. Since sizing materials presence oi too high 'vo'r tooi loi'vgav contentiof fifatci-ibns'in'th sults in open systems sin e'fiiape'r rately-pr epared aqueousdispersion of awet strength nesin g in cellulose-substantive for a g d d tb, pension" at an appropriate t v i r s s? developingtthe streng'theriingpropectxs ofcth'eresinthereonwg J.

t i' g kno a c inactivated; or, otherwise ,renderedQlessI efficient; by the Thef 'di'ssolved. sulfate ion 'c pncentr ationfior tion of these resins m most ins'tances;is

of about w to 1 5Qfparts per million andfpatticularly 30 parts per million. The optimum sulfate' ion concentration varies from resin to resm,;and'is most conve ot d t I ti mill makeup 'wat I 7 2,711,370 g Patented? Jun an 1955 a li e manufacture ofirosin sizedg wet strength paper; The proca of wet strength. resin are generally fresh river and well waters which frequently contain substantial amounts of dissolved sulfate ions, values of 50 to 250 parts per million being common. Moreover, discharge of this water frequently gives rise to stream pollution problems and in any event results in complete waste of the aluminum and'sulfate ions dissolved therein, together with the undersize cellulosicfines which are not retained on the screen when the fibrous suspension is sheeted.

The discovery has now been made that the dissolved sulfate ion content in paper-making system water can be readily controlled within optimum limits with substantially complete deposition of these sulfate values on the cellulose fibers in the form of valuable filling material by incorporating three steps in the normal paper-making process. In the first step, after the fibers have'been sized with rosin or similar material, sufiicient barium chloride is added to decrease the sulfate ion concentration in 'the cellulose fiber suspension to a value most desirable 'under the particular circumstances. This causes a precipitate of barium sulfate to form.

In the second step, a small amount of sodium aluminate is added, preferably together with a small amount of a neutral or alkaline sodium phosphate, or more advantageously still, the two materials are added together as the sodium phosphate aluminate of my U. S. Patent No. 2,431,946.

In the third step, the suspension is aged until a fine of aluminum hydrate has formed which absorbs the barium sulfate particles with any aluminum phosphate particles precipitated and carries them to the fibers together with a large part of the cellulose fiber fines present.

From the foregoing, it will be apparent that the present invention may be described broadly as a method for manufacturing sized, filled paper or other cellulosic web by forming a dilute aqueous suspension of paper-making cellulosic fibers, sizing the fibers therein by addition of 'an alum-precipitable sizing agent and alum thereto, adding barium chloride in amount at least about stoichiomet- 'rically equivalent to said alum, whereby the dissolved sulfate ions derived from said alum are precipitated as barium sulfate particles, adding a small amount of a sodium aluminate and aging the suspension, whereby a fioc of aluminum hydrate forms which adsorbs said barium sulfate particles and carries the same to the fibers, and sheeting and drying the fibers to form paper. As

f'stated, most advantageously the sodium aluminate is added in the form of sodium phosphate aluminate, whereby a coprecipitate of aluminum hydrate and aluminum -pho phate forms, the sodium phosphate constituent of the sodium phosphate aluminate reacting with the dissolved aluminum sulfate and forming a precipitate of finer particle size which is more readily adsorbed by the fibers.

' For the manufacture of wet strength, sized paper the process is performed as described, except that sufficient barium chloride is added to decrease the dissolved sulfate ion concentration to between about 30 and 150 parts per million, and an aqueous dispersion of a suitable wet strength resin in cellulose-substantive form is subsequently added after the action of the barium chloride and sodium aluminate is substantially complete.

Calculations show that in a paper mill employing fresh 'make-up water containing 50 parts per million of dissolved sulfate ions and recirculating its white water in a completely closed system, and manufacturing rosin sized paper by adding 2% of liquid rosin size and 3% of alum to a cellulose suspension at 1% consistency, the white :water reaches the maximum practical value of 800 parts per million of dissolved sulfate ions after about five cycles of use. Calculations further show that when thisprocedure is modified according to the present invention by the introduction of barium chloride and sodium aluminate as described, the water can be reused at least times before its dissolved sodium chloride and sulfate ion content interfere significantly with the rosin sizing process.

dry weight of the fibers.

in the suspension is then about parts per million.

'In'the third step, there is added 227 lb. of. solid or dissolved BaClz per million pounds of water to decrease 4 r The foregoing process has the following'principal ad vantages: a

l. The paper thus obtained has improved weight, opacity, and texture, but is otherwise indistinguishable so far as the user is concerned from paper produced in heretofore known manner.

2. The weight of filler in the paper is about equal to the weight .of barium chloride and sodium aluminate added. 3. The white water drained from the fibers during sheeting has'a desirably low dissolved sulfate ion content disposal of sodium chloride solution does not create a" stream pollution problem.

6. Typically, when operating according to the present invention so as to form paper containing 1%-3% by weight of rosin size, the paper produced contains about 2 /2%-6% by weight of filler. This amount of filler is sufiicient to give the paper distinctly improved weight and opacity while conferring the other advantages listed above. e

The present invention is capable of numerous distinct embodiments. Considering, for example, the manufacture of rosin sized paper, the alum and barium chloride may be added first, then the rosin size, and finally the sodium aluminate.

Alternatively, in this modification, the rosin size may be added first, before the alum. In the manufacture of rosin sized, wet strength paper the alum and barium chloride may be added first, then the rosin, then the sodium aluminate, alone or in conjunction with sodium phosphate, and finally the wet strength resin.

The common feature of these modifications when operating in batch procedure is that in the manufacture of sized paper, the sodium aluminate is added last, and in the manufacture of sized wet strength paper the sodium aluminate is added before the wet strength resin. In cyclic processes, where the amount of barium chloride added is sufficient to decrease the sulfate ion concentration to within the range tolerated well by the wet strength resin and the white water is recycled, the wet strength resin may be added first, this being equivalent to the foregoing embodiment where the wet strength resin is added last. i i

The process will be described step-wise in detailwith regard to a typicalpreferred embodiment suitable for 'render the fibers suitable for paper-making purposes.

The water at this point may have any ordinary sulfate ion content, and in this illustration it will be assumed that the suspension is prepared by the use of fresh, natural water containing 60 parts per million of dissolved sulfate ions as is frequently the case.

In the second step, the suspension is diluted to a con- .sistency of 0.6% by addition of more of the same water and the fibers are sized by addition of 1.5% of rosin size and 2.5% of papermakers alum, both based on the The sulfate ion concentration the dissolved sulfate ion concentration to the desirable value of 30 parts per million, this being a concentration i "at which most wet strength resins are efficiently adsorbed while ensuring that, "no bariumchlorideor other watersoluble barium salt will present precipitate of barium sulfa'te.forms'imrnediately.

In the fourth step, thei'e is added about0.4'% based on the dry weight of the'fibers of sodium phosphate aluminate, and the suspension aged about 3-10 nmates by gentle pumping through a large storage ta'nkjuntil formation of alumina hydratefloc is substantially 'coml plete and has carried the barium sulfate particles'to the fibers. p; In the fifth step, an: aqueous dispersion ofa cellulosesubstantive wet strength 'resinis added such as the amine 1 aldehyde resins shown,. for example, .in U. 'S; "Pat'ents No. 2,345,543, 2,407,376, 2,485,080, 2,559,22l, 2,582,840, 2,596,014, and 2,639,242, andafter adsorption of the' resin by the fibers the fibers are.formed into pa er. I i

The sizing agents and wet strength sresinsjernployed together with the methods by which these materials'are deposited on the fibers and thefibers are formed into paper or other cellulosic web are not particular features of the present invention. 5 i v The barium chloride may be added in anhydrous. or hydrated form and may be pre-dissolved, if desired, to. facilitate metering. According to the invention, the amount added is sufficient to decrease the sulfate :ion

content of the suspension to a desirable value. When fresh water of low sulfate ion content is available, about three mols of barium chloride is added per mol. of alum taken, this stoichiometric amount maintaining the sulfate ion concentration substantially constant. Where the water contains a large amount of dissolved sulfates, a larger initial addition of barium chloride is advantageously made to reduce the sulfate ion concentration to the desirable value, after which only suflieief'nt barium chloride need be added to precipitate the sulfate ions derived from the alum.

The sodium aluminate may be added in pure form,

but more advantageously will be added in admixture with a neutral or alkaline alkali metal such as di or" trisodium phosphate, or in the form of sodium aluminate phosphate. Only from about to by weight of the sodium aluminate need be added based on the dry weight of the fibers, this amount ensuring formation of sufficient to a'Fourdrinier machine. To the stock flowing through the headborr is added a dilute colloidal aqueous dispersion floc to adsorb the barium sulfate particles and cellulose fines and carry them to the fibers, while avoiding the danger of adding too little.

The amount of sodium phosphate (anhydrous basis) added is advantageously between about 25% of the weight of the sodium aluminate, this amount providing a large number of fine aluminum phosphate particles:

which act in the manner of nuclei promoting precipitation of the aluminum hydrate as a finely-divided floc.

In the present specification, it will be understood that the phrase sized paper" is used to designate paper com- The suspensi B a C-ls is added. su SP nsionis discharged the corresponding to 80% retention 'of these materials; The' wh'ite:water drained 'f ro mithe fibers during sheet-V ingcontains about; 60' parts p'er' million of dissolved .s ul-f I fateions' and is'suitabl e for reuse in the process described;

without addition ofmake-up water. 3 Q

ample The following illustrates 'the manufacture of resin- 7 sized, wet strength paperjcar 'ying about 3.7% by weight "of barium sulfate and aluminum'hydrate uniformly dispersed therethrough, while yielding a white water. of low,

dissolved ion content. I

. 2000 lb. of sulfate wood. pulp is beaten in fresh water 'containing 100 partsper million of dissolved sulfate-ions a and diluted'to 0.6%, consistency with thesame water. To the-suspension during beating is added .30 lb. (dry basis),

of liquid gum rosin size followed by lb. of papermakers alum, and, when the size has set, 96.0 lb. of, powdered BaClz. The suspension is discharged from the beater and 8.0 lb. of sodium phosphate aluminate as a 5% aqueous solution is'run into the .flow. The stock, now containing 40 parts per million of dissolved sulfate ions,

is pumped through a stock chest to provide an average retention period of 5 minutes and from'there is pumped of-the cationicmelamine-formaldehyde resin-of U.]S.

Patent No. 2,559,22l,-the preparation of which 'is more fully described in U. IS. Patent No. 2,345,543,- generally knownasParez607 resin,v at the rate of 2 lb. of the resin per '100 lb. of fiber, both c alculated on'the dr'y'basis.

The paper formed is heated. on rolls at 230 F. to dry the ,same' and develop the-strengthening properties of wet strength'resin'thereon. The drypaper obtained is wellsized papen of normalresistance to penetration by'water andof'normalwet strength. It contains 5.0% offiller (barium sulfate,'aluminum hydrate, and aluminum phosphate) correspondingto' 85% retention of both materials. Iclaim:

11A method for {manufacturing sized paper of im- 5 proved opacity and weight while'discharginga whitewater posed of cellulosic fibers having deposited thereon an effective amount of an alum-precipitable size, and that the weight of this size on the fibersis atleast 1% of the weight of the fibers.

The invention will be more particularly illustrated by the following examples. These examples are embodiments of the invention and are not to be construed in limitation thereon. 5 5

Example 1 The following illustrates the manufacture of rosinsized paper containing about 3% by Weight of filler resulting from the addition of barium chloride and sodium phosphate aluminate to an aqueous suspension of cellulosic fibers.

2000 lb. of sulfite wood pulp is beaten at 0.6% consistency in water containing parts per million of dissolved sulfate ions. The water is recirculated white water recovered from the manufacture of rosin-sized paper. To this suspension is added 30 lb. (dry basis) of having adissolved'sulfate ion content not materially greater than the dissolved sulfate ion content of the makeup water, which comprises forming a suspension of papermakingcellulosic fibers in makeup water, having a dis solved sulfate. ion content of less than about .800 parts per million, sizing said fibers in said suspension by addition or rosin size and'alum'thereto, adding barium chloride in-amount at least about stoichiometrically' equiv- ,alent to the-sulfate. content of said alum, whereby the dissolved sulfate ions introduced by said alum are precipitatedas barium sulfate particles,radding from abiout A phosphate selected from the group consisting of the neuf tralzand alkaline sodium phosphates is added with, the

liquid gum rosin size and 50lb. of papermakersalum.

After all the alum has dispersed, 52.5 lb. ofpowdered to Ed of sodium-aluminate based on the dry weightof the fibers, aging the suspension until a hoe of aluminum hydrate forms which .flocculateszand adsorbs said barium sulfate particles, andthe dissolved sulfateion content of the water is decreased-to a value not materially greater 7 than the .diss'olved sulfate ion content' of the make-up.

water, and sheetingand' drying said fibersto form paper. '2. A process according to claim' -1, wherein asodium sodium aluminate in amount equal to: about 25% .of the weight of. the sodium aluminate; w

3. A method for manufacturing sized, wet strength: paper while decreasing the dissolved sulfate ion concentration of the water to a desirably low value forbest adsorption of the Wet strength resin, which comprises form'- ing a suspension of paper-making cellulosio fibers Water having a dissol ed' sulfate ion content of about 1.0 to 150 parts per million, sizing said fibers in said suspension by addition of rosin size and alum thereto, addingbarium chloride in amount at least about stoichiometrically equival'ent to the sulfate content of said aluni or inamountsuflfieient to decrease the dissolvedi sulfate i'on content of the water to between about 30 and 1 50 parts per million,

whichever is greater, whereby aprecipitate of finelydivided'barium sulfate particles forms, adding fromabout A to /2 ofsodiumalmninatebased on the. dry. weight 15 of said fibers, aging said suspension until a fio'c': of alumi-- num hydrate forms which fiocc ulates and adsorbs said barium sulfate particles, then adding a cellulose-substantive wet strength resin in. colloidal. aqueousdispersiorr and adsorbingv said? resin on. said fibers, sheeting said fibers to form papen'.and heatirigsaid paper to dry the same and to develop the strengthening properties; of the resin. therein,

4. A' phosphate is addedwith the sodium aluminate in arno'unt equal to about 25% of the weight thereof.

References Cited in the file of this patent process. ac eording' to olaini. 3 wherein. asodium 

1. A METHOD FOR MANUFACTURING SIZED PAPER OF IMPROVED OPACITY AND WEIGHT WHILE DISCHARGING A WHITE WATER HAVING A DISSOLVED SULFATE ION CONTENT NOT MATERIALLY GREATER THAN THE DISSOLVED SULFATE ION CONTENT OF THE MAKEUP WATER, WHICH COMPRISES FORMING A SUSPENSION OF PAPERMAKING CELLULOSIC FIBERS IN MAKE-UP WATER HAVING A DISSOLVED SULFARE ION CONTENT OF LESS THAN ABOUT 800 PARTS PER MILLION, SIZING SAID FIBERS IN SAID SUSPENSION BY ADDITION OF ROSIN SIZE AND ALUM THERETO, ADDING BARIUM CHLORIDE IN AMOUNT AT LEAST ABOUT STOICHIOMETRICALLY EQUIVALENT TO THE SULFATE CONTENT OF SAID ALUM, WHEREBY THE DISSOLVED SULFATE IONS INTRODUCED BY SAID ALUM ARE PRECIPIITATE AS BARIUM SULFATE PARTICLES, ADDING FROM ABOUT 1/4% TO 1/2% OF SODIUM ALUMINATE BASED ON THE DRY WEIGHT OF THE FIBERS, AGING THE SUSPENSION UNTIL A FLOC OF ALUMINUM HYDRATE FORMS WHICH FLOCULATES AND ADSORBS SAID BARIUM SULFATE PARTICLES, AND THE DISSOLVED SULFATE ION CONTENT OF THE WATER IS DECREASED TO A VALUE NOT MATERIALLY GREATER THAN THE DISSOLVED SULFATE ION CONTENTS OF THE MAKE-UP WATER, AND SHEATING AND DRYING SAID FIBERS TO FORM PAPER. 